Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
  • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers

Definitions

• the present invention relates to a fluorinated elastic copolymer having excellent crosslinking reactivity, high fluidity, excellent compression set and base resistance, and a method for producing the same.
• Fluorine-containing elastic copolymers are excellent in heat resistance, chemical resistance, oil resistance, weather resistance, and the like, and are therefore applied even in harsh environments where ordinary hydrocarbon materials cannot withstand.
• Known fluorine-containing elastic copolymers include vinylidene fluoride / hexafluoropropylene copolymer, tetrafluoroethylene / propylene copolymer, and tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer. It has been.
• the tetrafluoroethylene / propylene copolymer is excellent in amine resistance and high temperature steam resistance as compared with the above-mentioned fluorinated elastic copolymer containing a repeating unit of vinylidene fluoride.
• a fluorinated elastic copolymer obtained by copolymerizing a monomer containing a crosslinkable functional group such as a vinyl ester monomer has been proposed (see Patent Document 2). reference).
• Patent Document 2 a fluorinated elastic copolymer obtained by copolymerizing a monomer containing a crosslinkable functional group such as a vinyl ester monomer has been proposed (see Patent Document 2). reference).
• the tetrafluoroethylene / propylene copolymer has insufficient fluidity in a cavity of a molding die when producing a product having a complicated shape.
• a fluorine-containing elastic copolymer obtained by copolymerizing tetrafluoroethylene / propylene in the presence of a fluorine-containing chain transfer agent having an iodine atom has also been proposed (see Patent Document 3).
• the polymerization rate was slow and the productivity of the fluorinated elastic copolymer was very low.
• the obtained fluorinated elastic copolymer has insufficient crosslinking reactivity, and various physical properties of the crosslinked rubber including compression set were not satisfactory.
• An object of the present invention is to provide a fluorinated elastic copolymer having excellent crosslinking reactivity, high fluidity, excellent heat resistance, chemical resistance and compression set resistance, and a method for producing the same.
• the present invention relates to a fluorinated elastic copolymer obtained by copolymerizing tetrafluoroethylene, propylene and, if necessary, perfluoro (alkyl vinyl ether), the fluorinated elastic copolymer Fluorine-containing elastic copolymer composition obtained by kneading 100 parts by mass, 30 parts by mass of carbon black, 5 parts by mass of triallyl isocyanurate, and 1 part by mass of 1,3-bis (tert-butylperoxyisopropyl) benzene
• the cross-linking characteristics were measured using a cross-linking characteristic measuring machine at 177 ° C.
• a fluorinated elastic copolymer having a difference (M H ⁇ M L ) value of 30 dN ⁇ m or more.
• the molar ratio of the repeating unit based on tetrafluoroethylene / the repeating unit based on propylene in the fluorinated elastic copolymer is 30/70 to 70/30.
• a fluorinated elastic copolymer is provided.
• the present invention also provides a fluorinated elastic copolymer containing an iodine atom and having a content of 0.01 to 5.0% by mass in the above fluorinated elastic copolymer.
• the present invention also includes a radical polymerization initiator and an iodine compound represented by the general formula RI 2 (wherein R is an alkylene group or a perfluoroalkylene group having 3 or more carbon atoms).
• R is an alkylene group or a perfluoroalkylene group having 3 or more carbon atoms.
• the present invention provides a method for producing the fluorinated elastic copolymer, wherein the copolymerization is carried out by emulsion polymerization in which the pH of the aqueous medium is in the range of 7 to 14 in the presence of an emulsifier in the aqueous medium.
• a method for producing a fluorinated elastic copolymer which is polymerization is provided.
• the present invention provides the method for producing a fluorinated elastic copolymer, wherein the RI 2 is 1,3-diiodopropane, 1,4-diiodobutane, 1,6-diiodohexane, 1,8-diiodine.
• the emulsifier may be represented by the general formula (1): R f1 OR f2 COOA (wherein R f1 is a perfluoroalkyl group having 1 to 8 carbon atoms).
• R f2 is a linear fluorine-containing alkylene group, and the fluorine-containing alkylene group may contain an etheric oxygen atom, and the fluorine-containing alkylene group has a carbon number of 1 to 3;
• a method for producing a fluorinated elastic copolymer which may have a side chain of a fluoroalkyl group, and A is a hydrogen atom, an alkali metal, or NH 4 . To do.
• the present invention provides the method of manufacturing a fluorinated elastic copolymer, wherein the emulsifier is represented by the general formula (2): F (CF 2 ) p O (CF (X) CF 2 O) q CF (X) COOA (In the formula, X represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, A represents a hydrogen atom, an alkali metal, or NH 4 , and p represents an integer of 1 to 10, q represents an integer of 0 to 3.)
• a method for producing a fluorinated elastic copolymer which is a fluorinated ether carboxylic acid compound represented by
• the present invention also provides a method for producing a fluorinated elastic copolymer, wherein the radical polymerization initiator is a redox polymerization initiator in the method for producing the fluorinated elastic copolymer.
• the present invention also provides the fluorinated elastic copolymer, ethylene tetrafluoride / ethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, and tetrafluoroethylene other than the fluorinated elastic copolymer.
• a fluorinated elastic copolymer composition containing at least one copolymer selected from the group consisting of a propylene copolymer and an ethylene-propylene-nonconjugated diene copolymer, Fluorine-containing elastic copolymer composition, wherein the content ratio of the polymer and the copolymer is fluorinated elastic copolymer / copolymer (mass ratio) 100/1 to 100/300 I will provide a.
• the fluorinated elastic copolymer of the present invention has excellent crosslinking reactivity, high fluidity, and excellent heat resistance, chemical resistance, and compression set resistance. In particular, it is excellent in injection moldability and suitable for products with complicated shapes. Moreover, the fluorinated elastic copolymer composition of the present invention is excellent in extrusion moldability and is suitable for a wire coating material.
• the fluorinated elastic copolymer of the present invention comprises tetrafluoroethylene (hereinafter referred to as TFE), propylene (hereinafter referred to as P), and optionally perfluoro (alkyl vinyl ether) (hereinafter referred to as PAVE).
• TFE tetrafluoroethylene
• P propylene
• PAVE optionally perfluoro (alkyl vinyl ether)
• the ratio of the repeating unit based on TFE and the repeating unit based on P is preferably 45/55 to 65/35, more preferably 50/50 to 60/40 (molar ratio).
• the ratio of the repeating unit based on TFE / the repeating unit based on P / the repeating unit based on PAVE in the obtained fluorinated elastic copolymer is 30 to 60/10 to 40 / It is preferably 10 to 40 (molar ratio).
• the fluorinated elastic copolymer of the present invention can be copolymerized with other monomers in addition to TFE, P, and PAVE as long as the effects of the present invention are not impaired.
• Other monomers include fluorinated olefins such as monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene and dichlorodifluoroethylene; hydrocarbons such as ethylene, 1-butene and isobutylene Examples include olefins; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether; vinyl esters such as vinyl acetate and vinyl propionate; vinyl chloride, vinylidene chloride, and trifluorostyrene.
• the iodine compound represented by the general formula RI 2 is an iodine compound in which iodine atoms are bonded to both ends of an alkylene group or a perfluoroalkylene group having 3 or more carbon atoms. It is. Specific examples include 1,3-diiodopropane, 1,4-diiodobutane, 1,6-diiodohexane, 1,8-diiodooctane, 1,3-diiodoperfluoropropane, 1,4-diiodopropane.
• Examples include iodoperfluorobutane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, and the like.
• the carbon number of the iodine compound represented by the general formula RI 2 is preferably 3 to 8.
• the iodine compound represented by the general formula RI 2 is more preferably an iodine compound having a perfluoroalkylene group, and most preferably 1,4-diiodoperfluorobutane.
• the iodine compound represented by the general formula RI 2 is preferably added so that the iodine atom content in the fluorinated elastic copolymer is 0.01 to 5.0% by mass. Further, it is particularly preferable to add so as to be 0.1 to 1.0% by mass.
• examples of the polymerization method include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, a bulk polymerization method and the like.
• an emulsion polymerization method in which monomers such as TFE and P are polymerized in an aqueous medium in the presence of an emulsifier is preferable because the molecular weight and the copolymer composition are easily adjusted and the productivity is excellent.
• the aqueous medium water or water containing a water-soluble organic solvent is preferable, and water containing a water-soluble organic solvent is more preferable.
• the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• tert-butanol, propylene glycol, and dipropylene glycol monomethyl ether are preferable, and tert-butanol is more preferable.
• the content of the water-soluble organic solvent in the aqueous medium is preferably 1 to 50 parts by mass and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of water.
• the pH of the aqueous medium is preferably 7 to 14, more preferably 7 to 11, further preferably 7.5 to 11, and most preferably 8 to 10.5.
• the pH of the aqueous medium should be in the above range during the entire polymerization period from the start of the polymerization to the end of the polymerization, but it may not be the total polymerization period. Preferably, it is 80% or more of the total polymerization period, more preferably 90% or more, and still more preferably 95% or more.
• pH buffering agents include inorganic salts.
• inorganic salts include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate, and carbonates such as sodium bicarbonate and sodium carbonate. More preferable specific examples of the phosphate include disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate.
• an ionic emulsifier is preferable and an anionic emulsifier is more preferable because the resulting fluorinated elastic copolymer latex is excellent in mechanical and chemical stability.
• an anionic emulsifier known ones can be used. Specific examples include hydrocarbon emulsifiers such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and fluorine-containing compounds such as ammonium perfluorooctanoate and ammonium perfluorohexanoate.
• Alcoic acid salt general formula (1): R f1 OR f2 COOA (wherein R f1 is a perfluoroalkyl group having 1 to 8 carbon atoms, R f2 is a linear fluorine-containing alkylene group, The fluorine-containing alkylene group may contain an etheric oxygen atom, the fluorine-containing alkylene group may have a side chain of a perfluoroalkyl group having 1 to 3 carbon atoms, A is a hydrogen atom, alkali metal or NH 4. fluorinated ether carboxylic acid compound represented by) (hereinafter, the general formula (1) that the compounds of) the elevation I can get lost.
• the carbon number of R f2 is preferably 1 to 12, and more preferably 1 to 8.
• a fluorine-containing emulsifier is preferable, and a fluorine-containing alkane salt or a compound of the general formula (1) is more preferable.
• An acid compound hereinafter referred to as a compound of the general formula (2) is most preferable.
• Examples of the compound represented by the general formula (1) or the compound represented by (2) when A is NH 4 include the following compounds.
• More preferable examples of the compound of the general formula (2) include F (CF 2 ) 2 OCF 2 CF 2 OCF 2 COONH 4 , F (CF 2 ) 2 O (CF 2 CF 2 O) 2 CF 2 COONH 4 , F (CF 2 ) 3 O (CF (CF 3 ) CF 2 O) 2 CF (CF 3 ) COONH 4 , F (CF 2 ) 3 OCF 2 CF 2 OCF 2 COONH 4 , F (CF 2 ) 3 O (CF 2 CF 2 O) 2 CF 2 COONH 4, F (CF 2) 4 OCF 2 CF 2 OCF 2 COONH 4, F (CF 2) 4 O (CF 2 CF 2 O) 2 CF 2 COONH 4, F (CF 2 ) 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 and the like.
• the content of the emulsifier is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the aqueous medium.
• the polymerization temperature in the method for producing a fluorinated elastic copolymer of the present invention is 0 ° C. to 50 ° C., preferably 10 ° C. to 40 ° C., more preferably 20 ° C. to 30 ° C.
• the polymerization temperature exceeds 50 ° C., the crosslinking reactivity of the resulting fluorinated elastic copolymer is remarkably lowered, which is not preferable.
• the polymerization temperature is within this range, the obtained fluorinated elastic copolymer is excellent in crosslinking reactivity, and the crosslinked rubber is excellent in mechanical properties.
• a water-soluble initiator and a redox polymerization initiator are preferable.
• the content of the radical polymerization initiator is preferably 0.0001 to 3% by mass and more preferably 0.001 to 1% by mass with respect to the total mass of the monomers.
• water-soluble initiators include persulfates (ammonium persulfate, sodium persulfate, potassium persulfate, etc.), organic initiators (disuccinic acid peroxide, azobisisobutylamidine dihydrochloride, etc.) and the like.
• Persulfates such as ammonium persulfate are preferred. In particular, ammonium persulfate is most preferable.
• the redox initiator a combination of persulfuric acid and a reducing agent may be mentioned.
• the redox initiator needs to be a polymerization initiator capable of polymerizing monomers such as TFE and P within a polymerization temperature range of 0 ° C to 50 ° C. is there.
• the persulfate include ammonium persulfate and alkali metal persulfates such as sodium persulfate and potassium persulfate. Particularly preferred is ammonium persulfate.
• examples of the reducing agent include thiosulfate, sulfite, bisulfite, pyrosulfite, hydroxymethanesulfinate, etc., preferably hydroxymethanesulfinate, most preferably hydroxymethanesulfinate.
• thiosulfate thiosulfate, sulfite, bisulfite, pyrosulfite, hydroxymethanesulfinate, etc., preferably hydroxymethanesulfinate, most preferably hydroxymethanesulfinate.
• a small amount of iron, a ferrous salt such as a ferrous salt, silver sulfate, or the like is present as a third component, and particularly preferably a water-soluble iron salt is allowed to coexist.
• water-soluble iron salts include ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, ferric chloride, ferrous ammonium sulfate, ferric sulfate Ammonium etc. are mentioned.
• a chelating agent is added in addition to the redox initiator system.
• the chelating agent ethylenediaminetetraacetic acid disodium salt is most preferable.
• the amount of persulfate used is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, particularly 0.05 to 0.5% by weight, based on the aqueous medium (100% by weight).
• the amount of the reducing agent used is preferably 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, and particularly preferably 0.05 to 0.5% by mass with respect to the aqueous medium (100% by mass). .
• the amount of iron, iron salt such as ferrous salt, and third component such as silver sulfate is preferably 0.0001 to 0.3% by mass with respect to the aqueous medium (100% by mass), 0.001 Is more preferably 0.1 to 0.1% by mass, and particularly preferably 0.01 to 0.1% by mass.
• the chelating agent is preferably 0.0001 to 0.3% by weight, more preferably 0.001 to 0.1% by weight, particularly 0.01 to 0.1% by weight based on the aqueous medium (100% by weight). preferable.
• the polymerization pressure in the method for producing a fluorinated elastic copolymer of the present invention is preferably 1.0 to 10 MPaG, more preferably 1.5 to 5.0 MPaG, and most preferably 2.0 to 4.0 MPaG.
• the polymerization rate is extremely low, which is not preferable. Within this range, the polymerization rate is appropriate and easy to control, and the productivity is excellent.
• the polymerization rate can be 10 to 100 g / L ⁇ hour.
• the polymerization rate is preferably 5 to 70 g / L ⁇ hour, more preferably 30 to 50 g / L ⁇ hour.
• the latex of the fluorinated elastic copolymer obtained by the emulsion polymerization method is aggregated by a known method to isolate the fluorinated elastic copolymer.
• the aggregation method include a method of salting out by adding a metal salt, a method of adding an inorganic acid such as hydrochloric acid, a method by mechanical shearing, a method by freezing / thawing, and the like.
• the fluorinated elastic copolymer of the present invention comprises 100 parts by mass of the fluorinated elastic copolymer, 30 parts by mass of carbon black, 5 parts by mass of triallyl isocyanurate, and 1,3-bis (tert-butylperoxyisopropyl).
• the cross-linking properties of the fluorinated elastic copolymer composition obtained by kneading 1 part by mass of benzene were measured using a cross-linking property measuring machine at 177 ° C. for 12 minutes under an amplitude angle of 3 degrees.
• the (M H ⁇ M L ) value which is the difference between the maximum torque value (M H ) and the minimum torque value (M L ), is 30 dN ⁇ m or more, preferably 35 dN ⁇ m or more, more preferably 38 dN. -M or more.
• t 90 (90% crosslinking time) representing the time required to reach 90% of the maximum value (M H ) of the torque is preferably 5 minutes or less, more preferably 4 minutes or less, and particularly preferably 3 .5 minutes or less, most preferably 3 minutes or less.
• the kneading can be performed under normal conditions by a rubber mixing device such as a roll, a kneader, a Banbury mixer, and an extruder, but kneading with two rolls is preferable.
• the Mooney viscosity of the fluorinated elastic copolymer of the present invention is preferably 5 to 200, more preferably 10 to 170, and most preferably 20 to 100.
• the Mooney viscosity is measured according to JIS K6300 using an L-shaped rotor with a diameter of 38.1 mm and a thickness of 5.54 mm at 100 ° C. with a preheating time of 1 minute and a rotor rotation time of 10 minutes. Is a measure of the molecular weight of Within this range, the balance between fluidity and crosslinkability is excellent.
• the glass transition temperature of the fluorinated elastic copolymer of the present invention is preferably -40 to 20 ° C, more preferably -20 to 10 ° C.
• the specific gravity of the fluorinated elastic copolymer of the present invention is preferably from 1.20 to 1.70, more preferably from 1.40 to 1.65.
• the fluorinated elastic copolymer obtained by the production method of the present invention is preferably crosslinked using an organic peroxide.
• organic peroxides include dialkyl peroxides (di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, ⁇ , ⁇ -bis (tert-butylperoxy) -p-diisopropylbenzene, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3, etc.), 1,1-di ( tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, benzoyl peroxide, tert-butylperoxybenzene, 2,5-dimethyl
• the amount of the organic peroxide used is preferably 0.3 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of the fluorinated elastic copolymer. Part is more preferable.
• the amount of the organic peroxide used is within this range, the crosslinking rate is appropriate, and the resulting crosslinked rubber is excellent in the balance between tensile strength and elongation.
• crosslinking aids include triallyl cyanurate, triallyl isocyanurate, trimethacryl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, m-phenylenediamine Bismaleimide, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, dipropargyl terephthalate, diallyl phthalate, N, N ', N ", N' ''-tetraallyl terephthalamide, containing vinyl group
• siloxane oligomers polymethylvinylsiloxane, polymethylphenylvinylsiloxane, etc.
• triallyl cyanurate, triallyl isocyanurate, and trimethallyl isocyanurate are examples of crosslinking aids.
• the addition amount of the crosslinking aid is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer.
• the crosslinking rate is appropriate, and the obtained crosslinked rubber is excellent in the balance between strength and elongation.
• the metal oxide is preferably a divalent metal oxide.
• Preferred examples of the divalent metal oxide include magnesium oxide, calcium oxide, zinc oxide, lead oxide and the like.
• the addition amount of the metal oxide is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer.
• the addition of the metal oxide can further improve the high cross-linking performance, which is a feature of the fluorinated elastic copolymer of the present invention.
• a pigment, a filler, a reinforcing agent, or the like for coloring the fluorinated elastic copolymer may be blended.
• fillers or reinforcing agents that are commonly used include carbon black, titanium oxide, silicon dioxide, clay, and talc.
• the fluorinated elastic copolymer of the present invention is blended with a polymer material other than the fluorinated elastic copolymer in accordance with the purpose to obtain a fluorinated elastic copolymer composition.
• polymer material examples include fluorine-containing resins such as polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, and tetrafluoroethylene / ethylene copolymers; vinylidene fluoride / propylene hexafluoride Copolymers, Tetrafluoroethylene / Propylene Copolymers Other than Fluorine-Containing Elastic Copolymers, Vinylidene Fluoride / Tetrafluoroethylene / Hexafluoropropylene Copolymers, Tetrafluoroethylene / Perfluoro (Alkyl Vinyl) Fluorine-containing elastomers such as ether) copolymers; Hydrocarbon elastomers such as ethylene-propylene-nonconjugated diene copolymers; and the like.
• fluorine-containing resins such as polytetrafluoroethylene, polyvinylid
• a fluorine-containing resin such as tetrafluoroethylene / ethylene copolymer
• the high crosslinkability and fluidity that are the characteristics of the fluorine-containing elastic copolymer of the present invention.
• the moldability and strength can be further improved.
• an elastomer such as an ethylene-propylene-nonconjugated diene copolymer
• the high crosslinkability characteristic of the fluorinated elastic copolymer of the present invention can be further improved.
• the polymer material contained in the fluorinated elastic copolymer composition of the present invention includes other than tetrafluoroethylene / ethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, and fluorinated elastic copolymer. Of these, at least one copolymer selected from the group consisting of a tetrafluoroethylene / propylene copolymer and an ethylene-propylene-nonconjugated diene copolymer is preferred.
• the fluorinated elastic copolymer composition of the present invention preferably contains the above-mentioned crosslinking aid and various fillers.
• fluorinated elastic copolymer of the present invention By uniformly mixing the fluorinated elastic copolymer of the present invention with an organic peroxide, a crosslinking aid, other various additives, etc., with a rubber mixing device such as a roll, a kneader, a Banbury mixer, or an extruder.
• a fluorinated elastic copolymer composition can be easily obtained.
• the fluorinated elastic copolymer composition is usually crosslinked simultaneously with molding by a method such as hot pressing, but may be crosslinked after being previously molded.
• a method such as hot pressing
• compression molding, injection molding, extrusion molding, calendar molding, dipping in a solvent, coating, or the like is employed.
• Various conditions such as hot press crosslinking, steam crosslinking, hot air crosslinking, and lead-based crosslinking are adopted as the crosslinking conditions in consideration of the molding method and the shape of the crosslinked product.
• the crosslinking temperature is preferably 100 to 400 ° C. and several seconds to 24 hours.
• secondary crosslinking is preferably employed for the purpose of improving mechanical properties and compression set of the crosslinked product and stabilizing other properties.
• the secondary crosslinking conditions are preferably 100 to 300 ° C. for 30 minutes to 48 hours.
• the fluorinated elastic copolymer composition can reduce the compression set.
• the compression set is preferably 50 or less, more preferably 40 or less, and even more preferably 35 or less.
• Glass transition temperature (°C) Glass transition temperature (°C)
• 10 ⁇ 0.1 mg of the fluorinated elastic copolymer is heated from ⁇ 50 ° C. to 150 ° C. at 10 ° C./min, and up to ⁇ 50 ° C. at 10 ° C./min.
• the center temperature of the endothermic peak change upon cooling was taken as the glass transition temperature.
• Mooney viscosity The Mooney viscosity of the fluorinated elastic copolymer is compliant with JIS K6300, using an L-shaped rotor having a diameter of 38.1 mm and a thickness of 5.54 mm, preheating time of 1 minute, and rotor rotation time of 4 minutes at 100 ° C. Measured with setting. Larger values indicate higher molecular weight indirectly.
• the specific gravity of the fluorinated elastic copolymer was measured by a method according to JIS K6220-1 using a specific gravity meter manufactured by Shinko Denshi.
• M H represents the maximum torque
• M L represents the minimum value of the torque
• M H -M L indicates the degree of crosslinking.
• the cross-linking characteristics serve as an index of cross-linking reactivity of the fluorinated elastic copolymer, and the larger the value of (M H ⁇ M L ), the better the cross-linking reactivity.
• the unit of torque is dN ⁇ m.
• t 10 and t 90 are 10% crosslinking time and the 90% crosslinking time, represents the time required to reach 10% and 90% of the maximum torque shown in crosslinking properties measured.
• the fluorine-containing elastic copolymer composition was hot-pressed at 170 ° C. for 20 minutes, and then subjected to secondary crosslinking in an oven at 200 ° C. for 4 hours to obtain a thickness of the fluorine-containing elastic copolymer composition.
• a 2 mm cross-linked rubber sheet was obtained.
• the obtained crosslinked rubber sheet was punched with a No. 3 dumbbell to prepare a sample. According to JISK6251, 100% tensile stress, tensile strength, and elongation at break were measured. Further, the hardness was measured according to JIS K6253.
• compression set The fluorinated elastic copolymer composition was subjected to a compression set test at 200 ° C. for 72 hours in accordance with JIS K6262, and the compression set was measured.
• Example 1 Production of fluorinated elastic copolymer A: After degassing the inside of a 3200 mL stainless steel pressure-resistant reactor equipped with an anchor blade for stirring, 1500 g of ion-exchanged water, 60 g of disodium hydrogenphosphate dodecahydrate, water 0.9 g of sodium oxide, 198 g of tert-butanol, 9 g of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as a fluorine-containing emulsifier, and 3.8 g of ammonium persulfate were added.
• EDTA ethylenediaminetetraacetic acid disodium salt dihydrate
• ferrous sulfate heptahydrate aqueous solution in which 0.4 g of ethylenediaminetetraacetic acid disodium salt dihydrate (hereinafter referred to as EDTA) and 0.3 g of ferrous sulfate heptahydrate were dissolved in 200 g of ion-exchanged water, Added to the reactor. At this time, the pH of the aqueous medium in the reactor was 9.5.
• EDTA ethylenediaminetetraacetic acid disodium salt dihydrate
• the anchor blade was rotated at 300 rpm and 6.4 g of 1,4-diiodoperfluorobutane was added.
• a 2.5% by mass aqueous solution of sodium hydroxymethanesulfinate dihydrate (hereinafter referred to as Rongalite) adjusted to pH 10.0 with sodium hydroxide (hereinafter referred to as Rongalit 2.5% by mass aqueous solution). .) was added to the reactor to initiate the polymerization reaction.
• Rongalite 2.5 mass% aqueous solution was continuously added to the reactor using a high-pressure pump.
• the latex of fluorinated elastic copolymer A was added to a 5% by mass aqueous solution of calcium chloride, and the latex of fluorinated elastic copolymer A was agglomerated by salting out to precipitate fluorinated elastic copolymer A.
• the fluorinated elastic copolymer A was filtered and recovered.
• the fluorinated elastic copolymer A was washed with ion-exchanged water and dried in an oven at 100 ° C. for 15 hours to obtain 880 g of a white fluorinated elastic copolymer A.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer A was 56/44 (molar ratio).
• the fluorinated elastic copolymer A had a Mooney viscosity of 80, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C.
• Table 1 shows the crosslinking properties and the physical properties of the crosslinked rubber of the fluorinated elastic copolymer A.
• Example 2 Fluorine-containing elastic copolymer in the same manner as in Example 1, except that the amount of 1,4-diiodoperfluorobutane added was 12.8 g and the total amount of the TFE / P monomer mixture gas was 800 g. A latex of B was obtained. The latex obtained had a pH of 7.8. The amount of Rongalite 2.5 mass% aqueous solution added was 90 g. The polymerization time was about 6 hours. In the same manner as in Example 1, 760 g of fluorinated elastic copolymer B was obtained from the latex of fluorinated elastic copolymer B.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer B was 56/44 (molar ratio).
• the fluorinated elastic copolymer B had a Mooney viscosity of 27, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C.
• Table 1 shows the crosslinking properties and crosslinked rubber properties of the fluorinated elastic copolymer B.
• Example 3 Production of fluorinated elastic copolymer C: It was produced in the same manner as in Example 1 except that 9 g of ammonium perfluorooctanoate was added instead of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as the fluorine-containing emulsifier. Latex was obtained. The obtained latex had a pH of 8.0. The addition amount of Rongalite 2.5 mass% aqueous solution was 85 g. The polymerization time was about 7 hours. In the same manner as in Example 1, 880 g of fluorinated elastic copolymer B was obtained from the latex of fluorinated elastic copolymer C.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer C was 56/44 (molar ratio).
• the fluorinated elastic copolymer C had a Mooney viscosity of 77, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C.
• Table 1 shows the crosslinking properties and crosslinked rubber physical properties of the fluorinated elastic copolymer C.
• Example 4 Production of fluorinated elastic copolymer D: A latex of fluorinated elastic copolymer D was obtained in the same manner as in Example 1 except that the polymerization temperature was 40 ° C. and the total amount of the TFE / P monomer mixed gas was 800 g. The resulting latex had a pH of 7.6. The amount of Rongalite 2.5 mass% aqueous solution added was 90 g. The polymerization time was about 6 hours. In the same manner as in Example 1, 780 g of fluorinated elastic copolymer B was obtained from the latex of fluorinated elastic copolymer D.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer D was 56/44 (molar ratio). Further, the fluorinated elastic copolymer D had a Mooney viscosity of 60, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C. Table 1 shows the crosslinking properties and crosslinked rubber physical properties of the fluorinated elastic copolymer D.
• Example 5 Production of fluorinated elastic copolymer E: A latex of fluorinated elastic copolymer E was obtained in the same manner as in Example 1 except that 4.4 g of 1,4-diiodobutane was added instead of 1,4-diiodoperfluorobutane. The resulting latex had a pH of 7.6. The amount of Rongalite 2.5 mass% aqueous solution added was 99 g. The polymerization time was about 7 hours. In the same manner as in Example 1, 880 g of fluorinated elastic copolymer E was obtained from the latex of fluorinated elastic copolymer E.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer E was 56/44 (molar ratio). Further, the fluorinated elastic copolymer E had a Mooney viscosity of 95, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C. Table 1 shows the crosslinking characteristics and physical properties of the crosslinked rubber of the fluorinated elastic copolymer E.
• Example 6 Production of fluorinated elastic copolymer F: A latex of fluorinated elastic copolymer F was obtained in the same manner as in Example 1, except that the polymerization temperature was 20 ° C. The pH of the obtained latex was 7.9. The addition amount of Rongalite 2.5 mass% aqueous solution was 85 g. The polymerization time was about 7 hours. In the same manner as in Example 1, 880 g of fluorinated elastic copolymer F was obtained from the latex of fluorinated elastic copolymer F.
• the ratio of the repeating unit based on TFE to the repeating unit based on P in the fluorinated elastic copolymer F was 56/44 (molar ratio).
• the fluorinated elastic copolymer F had a Mooney viscosity of 83, a specific gravity of 1.55, and a glass transition temperature of -3 ° C.
• Table 1 shows the cross-linking properties and physical properties of the cross-linked rubber of the fluorinated elastic copolymer F.
• Example 7 Production of fluorinated elastic copolymer H: Instead of 1,4-diiodoperfluorobutane, 7.8 g of 1,6-diiodoperfluorohexane was added, and the fluorine-containing elasticity was the same as in Example 1 except that the polymerization temperature was 30 ° C. A latex of copolymer H was obtained. The obtained latex had a pH of 7.5. The amount of Rongalite 2.5 mass% aqueous solution added was 90 g. The polymerization time was about 7 hours. In the same manner as in Example 1, 880 g of fluorinated elastic copolymer H was obtained from the latex of fluorinated elastic copolymer H.
• the ratio of the repeating unit based on TFE and the repeating unit based on P in the fluorinated elastic copolymer E was 56/44 (molar ratio).
• the fluorinated elastic copolymer H had a Mooney viscosity of 95, a specific gravity of 1.55, and a glass transition temperature of ⁇ 3 ° C.
• Table 1 shows the cross-linking characteristics and physical properties of the cross-linked rubber of the fluorinated elastic copolymer H.
• the anchor blade was rotated at 300 rpm and 6.4 g of 1,4-diiodoperfluorobutane was added.
• a 14.4% by mass aqueous solution of ammonium persulfate adjusted to pH 10.0 with sodium hydroxide was added to the reactor to initiate the polymerization reaction.
• the polymerization proceeds by maintaining a 14.4% by mass aqueous solution of ammonium persulfate at 75 ° C. using a high-pressure pump. As the polymerization proceeds, the pressure in the reactor decreases.
• the reactor internal temperature was cooled to 10 ° C., the polymerization reaction was stopped, and a latex of fluorinated elastic copolymer G was obtained. .
• the latex obtained had a pH of 7.0.
• the polymerization time was about 13 hours.
• the latex of the fluorinated elastic copolymer G is added to a 5% by mass aqueous solution of calcium chloride, the latex of the fluorinated elastic copolymer G is aggregated by salting out, and the fluorinated elastic copolymer G is precipitated.
• the fluorinated elastic copolymer G was filtered and recovered.
• the fluorinated elastic copolymer G was washed with ion-exchanged water and dried in an oven at 100 ° C. for 15 hours to obtain 770 g of a white fluorinated elastic copolymer G.
• the Mooney viscosity of the fluorinated elastic copolymer G was 30, the specific gravity was 1.55, and the glass transition temperature was ⁇ 3 ° C.
• Table 2 shows the cross-linking characteristics and physical properties of the cross-linked rubber of the fluorinated elastic copolymer G.
• Example 8 70 parts by mass of fluorinated elastic copolymer B, 30 parts by mass of fluorinated elastic copolymer J, 30 parts by mass of carbon black, 5 parts by mass of triallyl isocyanurate, and 1,3-bis (tert-butyl) 1 part by mass of peroxyisopropyl) benzene (trade name “Perkadox 14” manufactured by Kayaku Akzo Co., Ltd.) is kneaded with two rolls at room temperature for 10 minutes and uniformly mixed. A composition was obtained. Table 3 shows the crosslinking characteristics and the properties of the crosslinked rubber.
• Example 9 70 parts by mass of fluorinated elastic copolymer B, 30 parts by mass of “Aphras 150E” (trade name) manufactured by Asahi Glass Co., Ltd., 30 parts by mass of carbon black, 5 parts by mass of triallyl isocyanurate, 1,3-bis 1 part by mass of (tert-butylperoxyisopropyl) benzene (trade name “Perkadox 14”, manufactured by Kayaku Akzo Co., Ltd.) is kneaded with two rolls for 10 minutes at room temperature, and uniformly mixed with fluorine An elastic copolymer composition was obtained. Table 3 shows the crosslinking characteristics and the properties of the crosslinked rubber.
• Example 10 70 parts by mass of fluorinated elastic copolymer A, 30 parts by mass of “Esplen 505A” (trade name) manufactured by Sumitomo Chemical Co., Ltd., 30 parts by mass of carbon black, triethylene as an ethylene-propylene-nonconjugated diene copolymer 5 parts by mass of allyl isocyanurate and 1 part by mass of 1,3-bis (tert-butylperoxyisopropyl) benzene (manufactured by Kayaku Akzo Co., Ltd., trade name “Perkadox 14”) were mixed at room temperature with two rolls. Was kneaded for 10 minutes to obtain a uniformly mixed fluorinated elastic copolymer composition. Table 3 shows the crosslinking characteristics and the properties of the crosslinked rubber.
• the fluorinated elastic copolymer composition of Example 1 was excellent in fluidity and suitable for injection molding. Further, after heating, the crosslinked rubber made of the fluorinated elastic copolymer composition of Example 1 was easily removed from the mold, and no mold contamination was observed. On the other hand, the crosslinked rubbers made of the fluorinated elastic copolymer compositions of Comparative Example 1 and Comparative Example 2 do not easily peel from the mold because of insufficient crosslinking. The copolymer composition remained partially adhered.
• the fluorine-containing coelastic polymer of the present invention can be made into a crosslinked rubber by a crosslinking reaction.
• the crosslinked rubber is suitable for materials such as O-rings, sheets, gaskets, oil seals, diaphragms, and V-rings. It can also be applied to uses such as heat-resistant chemical-resistant sealing materials, heat-resistant oil-resistant sealing materials, wire coating materials, semiconductor device sealing materials, corrosion-resistant rubber paints, and urea-based grease sealing materials. In particular, since it is excellent in fluidity, it is suitable for use in rubber products having complicated shapes and products obtained by injection molding. The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-087936 filed on Mar. 28, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

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